Method for producing fatty acid alkyl ester and/or glycerin

ABSTRACT

In the method of the present invention for producing fatty acid alkyl ester and/or glycerin, as a heat source for an alcohol refining step of refining alcohol from unreacted alcohol that remains without reacting in a first reaction step, at least a part of heat of the unreacted alcohol is used. This allows reducing costs in production of fatty acid alkyl ester and/or glycerin over a solid catalyst.

TECHNICAL FIELD

The present invention relates to a method for producing fatty acid alkylester and/or glycerin. Specifically, the present invention relates torecycling of alcohol that is one of raw materials used in producingfatty acid alkyl ester and/or glycerin.

BACKGROUND ART

Fatty acid alkyl ester is widely used in the fields of cosmetics andmedicines, as well as fatty acid alkyl ester derived from animal fatsand vegetable oils is used in foods. Further, attention is paid to fattyacid alkyl ester serving as a fuel to be added to gas oil. In otherwords, this is a biodiesel fuel derived from animal fats and vegetableoils, which has been developed in order to reduce the amount of carbondioxide to be exhausted. Fatty acid alkyl ester is directly used as asubstitute for gas oil etc., or used as a fuel to be added to gas oiletc. with a certain ratio. The biodiesel fuel has various advantagessuch that it gives less damage to environment compared with aconventional diesel fuel derived from petroleum.

Further, glycerin is used mainly as a raw material for nitroglycerin,and also used in various fields such as a raw material for alkyd resin,medicines, foods, printing ink, cosmetics etc.

An example of a method for producing such fatty acid alkyl ester andglycerin is a method in which triglyceride that is a main component offat and oil is subjected to ester exchange with alcohol.

where R represents an alkyl group having 6-22 carbon atoms or an alkenylgroup having 6-22 carbon atoms with one or more unsaturated bonding.

In general, as the method with use of a transesterification between fatsand oils and alcohols, a method using a homogeneous alkaline catalyst isindustrially used.

However, usage of a homogeneous alkaline catalyst makes a step ofseparating and removing a catalyst complicated. Further, free fatty acidincluded in fat and oil is saponified by the alkaline catalyst andconsequently a soap is produced as a by-product. This requires a step ofcleaning the soap with a large amount of water and decreases the yieldof fatty acid alkyl ester due to emulsification of the soap. Further, astep of refining glycerin is complicated.

In order to solve the problem, there have been developed methods forproducing fatty acid alkyl ester and/or glycerin over a solid catalystinstead of a homogeneous alkaline catalyst (see Patent Documents 1-5 forexample). The method using the solid catalyst has a less complicatedprocess, and has a less amount of wastes such as waste water and wastesalts produced in the reaction, compared with the method using thehomogeneous alkaline catalyst. Further, Patent Document 6 discloses amethod for producing fatty acid alkyl ester and/or glycerin over a solidcatalyst.

Production of fatty acid alkyl ester and glycerin over the solidcatalyst does not require a complicated operation in its productionprocess, and has a less amount of wastes such as waste water and wastesalts produced in the reaction, compared with the method using thehomogeneous alkaline catalyst.

However, in general, a transesterification is an equilibrium reaction.Therefore, both in a case of the homogeneous alkaline catalyst and acase of the solid catalyst, it is necessary to use an excessive amountof a raw material (alcohol in general) in order to obtain a high yieldof a product.

Recently, in view of consideration on environment and reduction of costsfor production, it is requested that a material that can be reused byreproduction is reused as far as possible. Therefore, in producing fattyacid alkyl ester and glycerin, it is requested that out of an excessiveamount of alcohol used in the transesterification, unreacted alcoholthat remains without being used in the reaction is separated and refinedfrom a reaction liquid so as to be reused as a raw material. Forexample, Patent Document 7 discloses a method in which unreacted alcoholthat remains without being used in a reaction is evaporated from areaction liquid by a pressure flash and then refined as alcohol throughevaporation and reused as a raw material for a transesterification.

Patent Document 1: Japanese Unexamined Patent Publication No. Tokukai2005-200398 (published on Jul. 28, 2005)

Patent Document 2: Japanese Unexamined Patent Publication No. Tokukai2006-225352 (published on Aug. 31, 2006)

Patent Document 3: Japanese Unexamined Patent Publication No. Tokukai2005-177722 (published on Jul. 7, 2005)

Patent Document 4: Japanese Unexamined Patent Publication No. Tokukaihei7-173103 (published on Jul. 11, 1995)

Patent Document 5: French Patent Publication No. 2752242, specification

Patent Document 6: Japanese Unexamined Patent Publication No. Tokukai2005-206575 (published on Aug. 4, 2005)

Patent Document 7: U.S. Unexamined Patent Publication No. 2004/0034244,specification

Patent Document 8: U.S. Unexamined Patent Publication No. 2005/0113588,specification

DISCLOSURE OF INVENTION

However, in producing fatty acid alkyl ester and glycerin, a process forreusing, as a raw material, unreacted alcohol that remains without beingused in a reaction (the alcohol may be hereinafter referred to as“unreacted alcohol”) requires a very large amount of energy. That is,the process separately requires a cost for producing the very largeamount of energy and a cost for a device for producing the very largeamount of energy. Consequently, in producing fatty acid alkyl ester andglycerin, it is difficult to sufficiently obtain the effect of reducingcosts by reproducing and reusing alcohol.

The present invention was made in view of the foregoing problem. A mainobject of the present invention is to reduce production costs inproducing fatty acid alkyl ester and glycerin over a solid catalyst. Tobe more specific, an object of the present invention is to reduce energycosts for reusing unreacted alcohol in producing fatty acid alkyl esterand glycerin.

In a conventional method for producing fatty acid alkyl ester and/orglycerin over a solid catalyst, unreacted alcohol in a reaction liquidis evaporated as needed through a general method including evaporationetc. This is because the method with use of the solid catalyst uses anexcessive amount of alcohol compared with the method with use of thehomogeneous alkaline catalyst, and does not have a step of removingalcohol through water washing.

In general, fatty acid alkyl ester and/or glycerin derived from animalfats and plant oils have a high boiling point. Consequently, whenevaporating a small amount of alcohol remaining in the reaction liquidthrough evaporation etc., it is necessary to heat the reaction liquid ata high temperature. In this process, fatty acid alkyl ester andglyceride included in the reaction liquid are subjected to atransesterification, or fatty acid alkyl ester and glycerin aresubjected to the transesterification and as a result a reverse reactionoccurs in which fats and oils and alcohols are generated. The reversereaction not only decreases the yield of fatty acid alkyl ester and/orglycerin but also generates glyceride that is a reaction intermediate,so that the purity of fatty acid alkyl ester that is an end productdrops. In order to avoid a high temperature, evaporation in a highvacuum etc. is possible. However, since alcohol to be evaporated has alow boiling point in a high vacuum, it is necessary to increase theability of cooling instrument for condensing the alcohol.

As described above, in the conventional method for producing fatty acidalkyl ester and/or glycerin, it is impossible to produce high-qualityfatty acid alkyl ester and/or glycerin with a high yield and easiness.As such, a method for producing fatty acid alkyl ester and/or glycerinwith a high yield and easiness is requested.

The present invention was made in view of the foregoing problems. Anobject of the present invention is to produce high-quality fatty acidalkyl ester and/or glycerin with a high yield and easiness.

In order to achieve the foregoing object, the inventors of the presentinvention paid attention to the fact that a transesterification using asolid catalyst is performed at a high temperature and under a highpressure. The inventors of the present invention have diligently studiedand found that heat of unreacted alcohol evaporated from a reactionliquid obtained through the transesterification can be used as energynecessary for purifying alcohol from the unreacted alcohol, andcompleted the present invention.

The inventors further diligently studied and found that, whenevaporating unreacted alcohol from a reaction liquid obtained byreacting fats and oils with alcohols, use of an evaporator including aheat exchanger with a short residence time increases the yield andpurity of fatty acid alkyl ester that is an end product. Further, theinventors found that, when evaporating of alcohol in a glycerin phasethat is obtained in the first phase-separation step is performedsimultaneously with the evaporating of the unreacted alcohol, it ispossible to increase purity of glycerin that is another end product.Further, the inventors have found that sufficiently evaporating alcoholbefore the second phase-separation step reduces distribution of fattyacid alkyl ester to the glycerin phase, and increases the yield of thefatty acid alkyl ester.

Further, in a case where a solid catalyst is used as a catalyst inproducing fatty acid alkyl ester and/or glycerin as described above,there is a possibility that activity of the catalyst drops in a shorttime, which frequently requires troublesome exchanging of catalysts.

As an example for suppressing drop of activity of a solid catalyst,Patent Document 7 discloses a method for suppressing generation of freefatty acid in a transesterification system by restricting moistureconcentration in fat and oil and alcohol. However, the method disclosedin Patent Document 7 cannot sufficiently suppress deterioration of asolid catalyst, and therefore cannot provide a sufficient period for thesolid catalyst to perform well.

As described above, deterioration of a solid catalyst leads topreventing the increase in productivity of fatty acid alkyl ester and/orglycerin and preventing the cost reduction in producing fatty acid alkylester and/or glycerin. Therefore, there is a request for a method forproducing fatty acid alkyl ester and/or glycerin while preventingdeterioration in a solid catalyst.

The present invention was made in view of the foregoing problems. Anobject of the present invention is to provide a method for producingfatty acid alkyl ester and/or glycerin while sufficiently suppressingdrop in activity of a solid catalyst, i.e., lengthening the life of thesolid catalyst.

The inventors of the present invention have diligently studied whatsubstance deteriorates a solid catalyst, and found that one of thecauses for deterioration of a solid catalyst is covering of the surfaceof the solid catalyst in a transesterification, which covering is madeby at least one of phosphorous, phosphorous compounds, calcium, andcalcium compounds that are contained in fat and oil serving as areaction raw material.

In order to subject fat and oil to a chemical reaction (such astransesterification), it is general to perform a degum process in whicha gum component such as phospholipid and protein that is contained infat and oil is removed, as described in Patent Document 8. The degumprocess is a conventional and well-known process. Specifically, thedegum process is a process in which phosphorous acid, sulfuric acid,hydrochloric acid, boric acid, or citric acid and a gum componenthydrated by adding water to fat and oil are removed by centrifugalseparation. However, in the conventional degum process, it is impossibleto completely remove phospholipid contained in the fat and oil orphosphorous or phosphorous compounds that has been mixed in otherprocess, and consequently phosphorous atoms, i.e., approximately 5 ppmphosphorous or phosphorous compounds, remains in the fat and oil havingbeen subjected to the degum process. Further, calcium atoms, i.e.,approximately 2 ppm calcium or calcium compounds, also remains in thefat and oil having been subjected to the degum process.

That is, the inventors of the present invention have found that, in fatand oil having been subjected to only the conventional degum process,the surface of a solid catalyst is covered with at least one selectedfrom phosphorous, phosphorous compounds, calcium, and calcium compounds,and consequently the solid catalyst deteriorates.

The present invention was completed based on the above finding, andincludes the following subject matters.

The method of the present invention for producing fatty acid alkyl esterand/or glycerin includes a first reaction step of reacting fat and oilwith alcohol over a solid catalyst; a first alcohol stripping step ofevaporating, from a first reaction liquid obtained in the first reactionstep, unreacted alcohol that remains without reacting in the firstreaction step; and an alcohol refining step of refining the alcohol fromthe unreacted alcohol with use of at least a part of heat of theunreacted alcohol.

With the arrangement, at least a part of heat of the unreacted alcoholevaporated from the reaction liquid obtained in the first reaction stepof reacting the fat and oil with the alcohol over a solid catalyst isused in the alcohol refining step of refining the alcohol from theunreacted alcohol.

Thus, at least a part of energy required in the alcohol refining stepcan be obtained from heat generated inside the reaction system. That is,it is possible to reduce the amount of energy to be produced outside thereaction system. This yields the effect that costs in producing fattyacid alkyl ester and glycerin over a solid catalyst can be reduced.

In the present specification etc., “reaction system” indicates a seriesof steps of producing fatty acid alkyl ester and/or glycerin fromalcohol and fat and oil. That is, being “inside the reaction system”indicates being in a step of a series of steps of producing fatty acidalkyl ester and/or glycerin, and being “outside the reaction system”indicates being in a step other than a series of steps of producingfatty acid alkyl ester and/or glycerin.

It is preferable to arrange the method of the present invention so thatat least two stages of pressures that are different from each other areapplied in the first alcohol stripping step.

When at least two stages of pressures that are different from each otherare applied in evaporating the unreacted alcohol from the reactionliquid, it is possible to effectively use heat of the unreacted alcoholas an energy source in the reaction system. This yields the effect offurther reducing production costs in the method for producing fatty acidalkyl ester and/or glycerin over a solid catalyst.

It is preferable to arrange the method of the present invention so thata first stage of the pressures in the first alcohol stripping stepranges from 0.15 to 1.5 MPa.

When the first stage of the pressures in the first alcohol strippingstep is within the range, it is possible to evaporate, from the reactionliquid obtained in the first reaction step, a large part of theunreacted alcohol contained in the reaction liquid. Further, it ispossible to use heat of condensation of the evaporated unreacted alcoholas an energy source for the alcohol refining step.

It is preferable to arrange the method of the present invention tofurther include a second reaction step of reacting fat and oil withalcohol over a solid catalyst, the fat and oil being contained in anupper phase obtained by phase-separating refined products obtained inthe first alcohol stripping step; and a second alcohol stripping step ofevaporating, from a second reaction liquid obtained in the secondreaction step, unreacted alcohol that remains without reacting in thesecond reaction step, in the alcohol refining step, the alcohol beingrefined from the unreacted alcohol evaporated in the first and secondalcohol stripping steps, with use of at least a part of heat of theunreacted alcohol.

With the arrangement, at least a part of heat of the unreacted alcoholevaporated from the reaction liquid obtained in the second reaction stepof reacting fat and oil with alcohol over a solid catalyst is used inthe alcohol refining step, the fat and oil being contained in an upperphase obtained by phase-separating refined products obtained in thefirst alcohol stripping step.

This allows more amount of energy out of energy required in theproduction step to be obtained from heat generated within the reactionsystem. That is, it is possible to further reduce the amount of energyto be produced outside the reaction system. This allows further reducingproduction costs in producing fatty acid alkyl ester and/or glycerinover a solid catalyst.

It is preferable to arrange the method of the present invention so thatat least two stages of pressures that are different from each other areapplied in the second alcohol stripping step.

When at least two stages of pressures that are different from each otherare applied in evaporating the unreacted alcohol from the reactionliquid, it is possible to effectively use heat of the unreacted alcoholas an energy source in the reaction system. This yields the effect offurther reducing production costs in the method for producing fatty acidalkyl ester and/or glycerin over a solid catalyst.

It is preferable to arrange the method of the present invention so thata first stage of the pressures in the second alcohol stripping stepranges from 0.15 to 1.5 MPa.

When the first stage of the pressures in the second alcohol strippingstep is within the range, it is possible to evaporate, from the reactionliquid obtained in the second reaction step, a large part of theunreacted alcohol contained in the reaction liquid. Further, it ispossible to use heat of condensation of the evaporated unreacted alcoholas an energy source for the alcohol refining step.

It is preferable to arrange the method of the present invention so thata substance that is contained in the alcohol obtained in the alcoholrefining step and that is other than the alcohol accounts for not morethan 1000 ppm of all components contained in the alcohol obtained in thealcohol refining step.

When the substance that is contained in the alcohol and that is otherthan the alcohol is in the above range, it is possible to preferably usethe refined alcohol as a raw material for the transesterification.

It is preferable to arrange the method of the present invention tofurther include a first phase-separation step of phase-separating thefirst reaction liquid obtained in the first reaction step into a firstfatty acid alkyl ester phase and a first glycerin phase; a secondreaction step of reacting fat and oil contained in the first fatty acidalkyl ester with alcohol over a solid catalyst; a third alcoholstripping step of evaporating, from a second reaction liquid obtained inthe second reaction step, unreacted alcohol that remains withoutreacting in the second reaction step, with use of an evaporatorincluding a heat exchanger selected from a thin film evaporator with anagitating rotor, a thin film evaporator with tubes arranged as a bundle,and a thin film evaporator with a centrifugal rotor; and a secondphase-separation step of phase-separating refined products obtained inthe third alcohol stripping step into a second fatty acid alkyl esterphase and a second glycerin phase.

With the arrangement, in the first reaction step, the fat and oil andthe alcohol are caused to react with each other over a solid catalyst,thereby producing the first reaction liquid containing fatty acid alkylester, glycerin, unreacted fat and oil, unreacted alcohol, and areaction intermediate such as glyceride. Then, in the firstphase-separation step, the first reaction liquid is separated, therebyobtaining the first fatty acid alkyl ester phase containing fatty acidalkyl ester, unreacted fat and oil, unreacted alcohol, and the reactionintermediate, and the first glycerin phase containing glycerin andunreacted alcohol. Further, in the second reaction step, the first fattyacid alkyl ester phase and the alcohol are caused to react with eachother, thereby obtaining the second reaction liquid containing fattyacid alkyl ester, glycerin, and unreacted alcohol.

Subsequently, in the alcohol stripping step, the unreacted alcohol isevaporated from the second reaction liquid with use of the evaporatorincluding a heat exchanger with a short residence time. Finally, therefined products are phase-separated in the second phase-separationstep, thereby obtaining the second fatty acid alkyl ester phasecontaining fatty acid alkyl ester and the second glycerin phasecontaining glycerin.

With the arrangement, in the third alcohol stripping step, the alcoholis evaporated with use of the evaporator including the heat exchangerwith a short residence time. Consequently, it is possible to preventexcessively heating fatty acid alkyl ester and/or glycerin that is to bean end product, thereby preventing reverse reaction from proceeding.Further, since the alcohol is sufficiently removed from the materials(the refined products) to be phase-separated in the secondphase-separation step, it is possible to prevent fatty acid alkyl esterfrom being distributed to the second glycerin phase, thereby preventingdrop of the yield of fatty acid alkyl ester, and omitting refining afterthe phase-separation.

As described above, with the arrangement, it is possible to producehigh-quality fatty acid alkyl ester and/or glycerin with high yield andwith easiness.

Further, it is preferable to arrange the method so that the residencetime is 20 minutes or less. When the residence time is 20 minutes orless, the above effect can be yielded.

It is preferable to arrange the method of the present invention so thatin the third alcohol stripping step, the unreacted alcohol that remainswithout reacting in the first reaction step is further evaporated fromthe first glycerin phase with use of the evaporator.

With the arrangement, the alcohol can be evaporated from the secondreaction liquid and the first glycerin phase with use of one evaporator.Here, the evaporator for evaporating the alcohol from the first glycerinphase may be the evaporator used in the steps in the above productionmethod. With the arrangement, particularly in the evaporator forevaporating the alcohol from the second reaction liquid, the alcohol isevaporated from the first glycerin phase as well as from the secondreaction liquid. An example of a method for evaporating the alcohol fromthe first glycerin phase is a method for evaporating alcohol before thefirst phase-separation step. In order to make alcohol concentration inglycerin not more than 1%, it is necessary to heat a reaction liquidcontaining fatty acid alkyl ester and glycerin for a long time. Thiscauses reverse reaction in the transesterification, which is notpreferable. Further, Patent Document 1 discloses a production method inwhich an evaporator for the second reaction liquid is not used for anevaporator for evaporating alcohol from the first glycerin phase.However, this requires providing an additional evaporator and anadditional separator, which is not preferable.

Further, with the arrangement of the present invention, the alcohol isevaporating from the first glycerin phase with use of the evaporator.Consequently, when an end product is obtained from the first glycerinphase as well as from the second reaction liquid, it is possible toprevent excessive heating, thereby preventing reverse reaction. Further,it is possible to sufficiently remove the alcohol from the material tobe phase-separated in the second phase-separation step, so that it ispossible to prevent fatty acid alkyl ester from being distributed to thesecond glycerin phase, thereby preventing drop of the yield of fattyacid alkyl ester, and omitting refining after the phase-separation.

It is preferable to arrange the method of the present invention so thatin the third alcohol stripping step, the unreacted alcohol that remainswithout reacting in the second reaction step is evaporated from thesecond reacting liquid obtained in the second reaction step, and theunreacted alcohol that remains without reacting in the first reactionstep is evaporated from the first glycerin phase.

It is preferable to arrange the method of the present invention so thata second alcohol stripping step of evaporating unreacted alcohol fromthe second reaction liquid is performed before the third alcoholstripping step.

With the arrangement, before the third alcohol stripping step, theunreacted alcohol that remains without reacting in the second reactionstep is evaporated from the second reaction liquid in the secondreaction step. This reduces the amount of alcohol contained in amaterial to be evaporated in the third alcohol stripping step, therebyevaporating the unreacted alcohol with further higher efficiency.

It is preferable to arrange the method of the present invention so thatthe first alcohol stripping step is performed before the firstphase-separation step.

With the arrangement, the amount of alcohol contained in a material tobe evaporated in the third alcohol stripping step is reduced, therebyevaporating the unreacted alcohol with further higher efficiency.

It is preferable to arrange the method of the present invention so thatin the third alcohol stripping step, the unreacted alcohol is evaporatedin such a manner that the unreacted alcohol accounts for not more than0.5 wt % of the refined products obtained in the third alcohol strippingstep.

With the arrangement, the unreacted alcohol accounts for not more than0.5 wt % of the refined products obtained in the alcohol stripping step,so that it is possible to prevent fatty acid alkyl ester from beingdistributed to the second glycerin phase, thereby preventing drop in theyield of fatty acid alkyl ester, and it is possible to omit refiningafter the phase-separation. Therefore, with the arrangement, it ispossible to produce high-quality fatty acid alkyl ester and/or glycerinwith high yield and with easiness.

It is preferable to arrange the method of the present invention so as tofurther include a removal step of removing at least one selected fromphosphorous, phosphorous compounds, calcium, and calcium compounds thatare contained in a reaction raw material including the fat and oil andthe alcohol.

With the arrangement, at least one selected from phosphorous,phosphorous compounds, calcium, and calcium compounds that are containedin the reaction raw material is removed before the reaction step.

This allows preventing at least one selected from phosphorous,phosphorous compounds, calcium, and calcium compounds from covering thesurface of the solid catalyst, so that it is possible to suppress dropof activity of the solid catalyst due to the covering by at least oneselected from phosphorous, phosphorous compounds, calcium, and calciumcompounds. In other words, it is possible to lengthen the life of thesolid catalyst.

Further, by suppressing drop of activity of the solid catalyst, it ispossible to reduce frequency of troublesome exchanging of a solidcatalyst with dropped activity in producing fatty acid alkyl esterand/or glycerin.

Further, since the life of the solid catalyst is lengthened, it ispossible to increase the amount of fatty acid alkyl ester and/orglycerin generated with respect to the same amount of the solidcatalyst. This allows reducing the cost for the solid catalyst withrespect to each product, and increasing productivity of fatty acid alkylester and/or glycerin.

It is preferable to arrange the method of the present invention so thatin the removal step, at least one selected from phosphorous, phosphorouscompounds, calcium, and calcium compounds is adsorbed and removed by anadsorber.

With the arrangement, it is possible to effectively remove at least oneselected from phosphorous, phosphorous compounds, calcium, and calciumcompounds.

It is preferable to arrange the method of the present invention so thatin the removal step, concentration of phosphorous atoms in phosphorousand phosphorous compounds contained in the reaction raw material is lessthan 2.5 ppm.

By setting the concentration of phosphorous atoms in phosphorous andphosphorous compounds contained in the fat and oil and the alcohol inthe reaction step to be in the above range, it is possible to furtherprevent covering of the surface of the solid catalyst by phosphorousand/or phosphorous compounds.

It is preferable to arrange the method of the present invention so thatin the removal step, concentration of calcium atoms in calcium andcalcium compounds contained in the reaction raw material is less than 1ppm.

By setting the concentration of calcium atoms in calcium and calciumcompounds contained in the fat and oil and the alcohol in the reactionstep to be in the above range, it is possible to further preventcovering of the surface of the solid catalyst by calcium and/or calciumcompounds.

It is preferable to arrange the method of the present invention so as tofurther include a first phase-separation step of phase-separatingrefined products into a first fatty acid alkyl ester phase and a firstglycerin phase with use of a separation filter which is so calledcoalescer, the refined product being obtained by evaporating theunreacted alcohol from the first reaction liquid in the first alcoholstripping step; a second reaction step of reacting fat and oil containedin the first fatty acid alkyl ester phase with alcohol over a solidcatalyst; and a second phase-separation step of phase-separating asecond reaction liquid obtained in the second reaction step into asecond fatty acid alkyl ester phase and a second glycerin phase with useof a separation filter.

With the arrangement, it is possible to very promptly and sufficientlyperform phase-separation between the upper phase and the lower phase.This allows increasing the yield of fatty acid alkyl ester that is anend product, and lengthening the life of the solid catalyst used in thesecond reaction step.

In order to solve the foregoing problem, the device of the presentinvention for producing fatty acid alkyl ester and/or glycerin includes:a reactor for reacting fat and oil with alcohol over a solid catalyst; astripper for stripping, from a reaction liquid obtained in the reactor,unreacted alcohol that remains without reacting in the reactor; and arefiner for refining the alcohol from the unreacted alcohol stripped inthe stripper, with use of at least a part of heat of the unreactedalcohol.

It is preferable to arrange the device of the present invention tofurther include a packed device filled with an adsorber for adsorbing atleast one selected from phosphorous, phosphorous compounds, calcium, andcalcium compounds that are contained in a reaction raw materialincluding the fat and oil and the alcohol, the reactor causing thereaction raw material having passed the packed device to react over asolid catalyst.

Additional objects, features, and strengths of the present inventionwill be made clear by the description below. Further, the advantages ofthe present invention will be evident from the following explanation inreference to the drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a drawing schematically illustrating a device for producingfatty acid alkyl ester and/or glycerin.

FIG. 2 is a drawing schematically illustrating a device for producingfatty acid alkyl ester and/or glycerin.

FIG. 3 is a graph showing changes of the conversion rates of palm oiland the yields of fatty acid methyl ester in Example 5 and ComparativeExample 5.

REFERENCE NUMERALS

-   1. Production device-   2. Fat and oil storage tank-   3. Alcohol storage tank-   4. Waste storage tank-   5. Fatty acid alkyl ester storage tank-   6. Glycerin storage tank-   10. First reactor-   11. First high pressure flash tower-   12. First low pressure flash tower-   13. Alcohol refining tower-   14. First phase separator-   20. Second reactor-   21. Second high pressure flash tower-   22. Second low pressure flash tower-   23. Alcohol evaporator-   24. Second phase separator-   25. Packed device-   29. Solid-liquid separator 30, 31. Heat exchanger

BEST MODE FOR CARRYING OUT THE INVENTION

A method for producing fatty acid alkyl ester and/or glycerin isdescribed below in accordance with an embodiment of the presentinvention. “Fatty acid alkyl ester and/or glycerin” in the presentspecification etc. is synonymous with “at least one of fatty acid alkylester and glycerin.”

The method of the present embodiment for producing fatty acid alkylester and/or glycerin mainly includes a first reaction step, a secondreaction step, a first phase-separation step, a second phase-separationstep, a first alcohol stripping step, a second alcohol stripping step, athird alcohol stripping step, an alcohol refining step, a removal step,and a solid-liquid separating step. These steps are detailed later.

(Process for Producing Fatty Acid Alkyl Ester and/or Glycerin)

With reference to FIG. 1, the following explains a process for producingfatty acid alkyl ester and/or glycerin, including the above steps. FIG.1 is a drawing schematically illustrating a production device of thepresent invention for producing fatty acid alkyl ester and/or glycerin.

As illustrated in FIG. 1, a production device 1 for producing fatty acidalkyl ester and/or glycerin mainly includes a fat and oil storage tank2, alcohol storage tank 3, a waste storage tank 4, a fatty acid alkylester storage tank 5, a glycerin storage tank 6, a first reactor 10, afirst high pressure flash tower 11, a first low pressure flash tower 12,an alcohol refining tower 13, a first phase separator 14, a secondreactor 20, a second high pressure flash tower 21, a second low pressureflash tower 22, an alcohol evaporator 23, a second phase separator 24, aheat exchanger 30, a heat exchanger 31, and lines connecting thesemembers.

As illustrated in FIG. 1, alcohol is supplied from the alcohol storagetank 3 to the first reactor 10, and fat and oil are supplied from thefat and oil storage tank 2 to the first reactor 10. In this process, thefat and oil and the alcohol are heated and pressured before beingsupplied to the first reactor 10 filled with a solid catalyst. The firstreactor 10 and the first reaction step in the first reactor 10 aredetailed later.

A first reaction liquid containing fatty acid alkyl ester, glycerin,unreacted part of the above fat and oil, unreacted part of the abovealcohol, and a reaction intermediate such as glyceride is obtained bypassing the first reactor 10 and is supplied to the first high pressureflash tower 11. The first high pressure flash tower 11 evaporates theunreacted alcohol from the first reaction liquid, and the evaporatedunreacted alcohol is supplied to the heat exchanger 30. The reactionliquid from which the unreacted alcohol has been evaporated is suppliedto the first low pressure flash tower 12. The first low pressure flashtower 12 evaporates the unreacted alcohol from the first reactionliquid, and the evaporated unreacted alcohol is supplied to the alcoholrefining tower 13. The reaction liquid from which the unreacted alcoholhas been evaporated in the first low pressure flash tower 12 is suppliedto the first phase separator 14. The first alcohol stripping step in thefirst high pressure flash tower 11 and the first low pressure flashtower 12 are detailed later.

Subsequently, the heat exchanger 30 recovers heat of the unreactedalcohol supplied thereto, and the unreacted alcohol from which the heathas been recovered is supplied to the alcohol refining tower 13. Thealcohol refining tower 13 refines alcohol from the unreacted alcoholwith use of the heat having been recovered from the unreacted alcohol inthe heat exchanger 30. The refined alcohol is supplied to the alcoholstorage tank 3 and is reused as a raw material. Further, a waste liquidcontaining components other than the alcohol is exhausted from theproduction device and is stored in the waste storage tank 4. The heatexchanger 30 and the alcohol refining tower 13 and the alcohol refiningstep in the alcohol refining tower 13 are detailed later.

On the other hand, the reaction liquid from which the unreacted alcoholhas been evaporated is supplied to the first phase separator 14 and isphase-separated by the first phase separator 14 into a fatty acid alkylester phase (upper phase, hydrophobic phase) and a glycerin phase (lowerphase, hydrophilic phase) (first phase-separation step). A first fattyacid alkyl ester phase in the upper phase is mixed with alcohol suppliedfrom the alcohol storage tank 3 and is supplied to the second reactor20. Thus, unreacted fat and oil contained in the fatty acid alkyl esterphase are completely reacted. The second reactor 20 and the secondreaction step in the second reactor 20 are detailed later.

A second reaction liquid containing fatty acid alkyl ester, glycerin,and unreacted alcohol is obtained by passing the second reactor 20 andis supplied to the second high pressure flash tower 21. The second highpressure flash tower 21 evaporates the unreacted alcohol from the secondreaction liquid, and the evaporated unreacted alcohol is supplied to theheat exchanger 31. The second reaction liquid from which the unreactedalcohol is evaporated is supplied to the second low pressure flash tower22. The second low pressure flash tower 22 evaporates the unreactedalcohol contained in the reaction liquid, and the evaporated unreactedalcohol is supplied to the alcohol storage tank 3 and reused as a rawmaterial. The second reaction liquid from which the unreacted alcoholhas been removed in the second low pressure flash tower 22 is suppliedto the alcohol evaporator 23. The second alcohol stripping step in thesecond high pressure flash tower 21 and the second low pressure flashtower 22 is detailed later.

Subsequently, the heat exchanger 31 recovers heat of the unreactedalcohol supplied thereto, and the unreacted alcohol from which the heathas been recovered is supplied to the alcohol storage tank 3. On theother hand, the second reaction liquid from which the unreacted alcoholhas been evaporated and the first glycerin contained in the glycerinphase separated by the first phase separator 14 are supplied to thealcohol evaporator 23, and unreacted alcohol contained in the suppliedsecond reaction liquid and in the supplied glycerin is furtherevaporated by the alcohol evaporator 23. The evaporated unreactedalcohol is supplied to the alcohol refining tower 13 and reused asalcohol.

A refined product obtained by evaporating the unreacted alcohol from thesecond reaction liquid and the lower phase obtained in the firstphase-separation step (first glycerin phase) in the alcohol evaporator23 is supplied to the second phase separator 24. The second phaseseparator 24 phase-separates the supplied refined product into a fattyacid alkyl ester phase (upper phase, hydrophobic phase) and a glycerinphase (lower phase, hydrophilic phase). The second fatty acid alkylester phase that is the upper phase is supplied to the fatty acid alkylester storage tank 5, and the second glycerin phase that is the lowerphase is supplied to the glycerin storage tank 6.

Note that a series of steps in a “reaction system” refer to the whole ofa series of the above process steps. That is, all of process steps otherthan the above process steps are outside the “reaction system.”

(Details of First Reaction Step and Second Reaction Step)

The following details the first reaction step and the second reactionstep. Each of the first and second reaction steps is a step ofgenerating fatty acid alkyl ester and/or glycerin by mixing a fat andoil with alcohol and subjecting the mixture to a transesterificationover a solid catalyst.

In the transesterification, it is possible to simultaneously obtainfatty acid alkyl ester and glycerin, and therefore it is possible toindustrially and easily obtain refined glycerin useful as a chemicalmaterial for various purposes and fatty acid alkyl ester useful for abiodiesel fuel. Solid catalysts, alcohols, and fats and oils that may bepreferably used in the present invention are detailed later.

A temperature of a mixture solution of the fat and oil and the alcoholin the first reactor 10 and the second reactor 20, i.e., a reactiontemperature preferably ranges from 100 to 300° C., more preferablyranges from 120 to 270° C., and further preferably ranges from 150 to235° C. When the reaction temperature is within the above range, it ispossible to sufficiently increase a reaction speed and to sufficientlyprevent decomposition of the alcohol.

Pressures in the first reactor 10 and the second reactor 20, i.e.,reaction pressures preferably range from 0.1 to 10 MPa, more preferablyrange from 0.2 to 9 MPa, and further preferably range from 0.3 to 8 MPa.When the reaction pressure is within the above range, it is possible tosufficiently increase the reaction speed and to sufficiently prevent aside reaction. When the reaction pressure exceeds 10 MPa, a specialdevice resistible under a high pressure is required and thereforeadditional costs such as equipment costs are required.

The amounts of the alcohol and the amount of the fat and oil that are tobe supplied to the first reactor 10 and the second reactor 20 are suchthat the amount of the alcohol relative to the amount of the fat and oilpreferably range from 1 to 30 times larger than the theoreticallyrequired amount, more preferably range from 1.2 to 20 times larger thanthe theoretically required amount, and still more preferably range from1.5 to 15 times larger than the theoretically required amount, andfurther preferably range from 2 to 10 times larger than thetheoretically required amount. When the amount of the alcohol relativeto the amount of the fat and oil is within the range, it is possible tocause the fat and oil and the alcohol to sufficiently react with eachother, and to sufficiently increase a conversion rate of the fat andoil. Further, it is possible to reduce the amount of the collectedalcohol in the first alcohol stripping step or the second alcoholstripping step and to reduce utility costs necessary for the alcoholrefining tower 13 or the alcohol evaporator 23, so that it is possibleto reduce production costs.

The theoretically required amount of alcohol in the presentspecification etc. refers to the number of moles of the alcohol withrespect to a saponification value of a fat and oil, and is calculated inaccordance with the following equation.

Theoretically required amount of alcohol (g)=amount of molecules ofalcohol×[amount of used fat and oil (g)×saponification value (mg (KOH)/g(fat and oil)/56100)

The shape of each of the first reactor 10 and the second reactor 20 maybe either a batch type or a fixed bed flow type. However, it ispreferable that the shape is a fixed bed flow type. When each of thefirst reactor 10 and the second reactor 20 is a fixed bed reactiondevice filled with a solid catalyst, a step for separating a catalyst isunnecessary. This allows omitting a troublesome work, making industrialproduction easier. When each of the first reactor 10 and the secondreactor 20 is a fixed bed reaction device or a batch reaction tank,conditions such as a reaction time may be conventional and well-knownconditions.

In a case where the fat and oil contain impurities such as phospholipidand protein, there may be provided a degumming reaction tank forperforming a degumming process in which the impurities are removed byadding mineral acid. It is preferable that the degumming reaction tankis provided at a stage prior to the first reactor 10. It is morepreferable that the degumming reaction tank is provided at a stage priorto the mixing of the fat and oil with the alcohol.

(Details of the First and Second Alcohol Stripping Steps)

The following details the first and second alcohol stripping steps. Thefirst and second alcohol stripping steps are steps of evaporatingunreacted alcohols from the reaction liquids obtained in the first andsecond reaction steps, respectively.

It is preferable that each of the first and second alcohol strippingsteps is performed with at least two stages of pressures that aredifferent from each other. With reference to FIG. 1, a refinement at thefirst stage is a refinement in the first high pressure flash tower 11 orthe second high pressure flash tower 21, and a refinement at the secondstage is a refinement in the first low pressure flash tower 12 or thesecond low pressure flash tower 22.

A pressure of the refinement at the first stage in the first and secondalcohol stripping steps, i.e., a pressure of the first high pressureflash tower 11 or the second high pressure flash tower 21 preferablyranges from 0.15 to 1.5 MPa, and more preferably ranges from 0.20 to 1.0MPa. Further, it is preferable that a pressure of the first low pressureflash tower 12 or the second low pressure flash tower 22 is a normalpressure.

“Normal pressure” in the present specification etc. means a pressureranging from 0.095 to 0.105 MPa.

When the pressure at the first stage in the first and second alcoholstripping steps is within the above range, the unreacted alcoholcontained in the reaction liquid can be sufficiently evaporated.Further, when the pressure at the first stage in the first and secondalcohol stripping steps is within the above range, it is possible tocollect the unreacted alcohol at a temperature higher than a boilingpoint (at a normal pressure). Thus, heat of condensation of theunreacted alcohol can be used in the alcohol refining step.

In the present embodiment, each of the first and second alcoholstripping steps is refinement with two stages. However, the presentinvention is not limited to this, and each of the first and secondalcohol stripping steps may be refinement with one stage or refinementwith three or more stages.

However, each of the first and second alcohol stripping steps ispreferably refinement with two or more stages, since this case allowseffectively using heat of the unreacted alcohol as an energy sourceinside the reaction system. For example, in the case where each of thefirst and second alcohol stripping steps is refinement with two stages,the heat of the unreacted alcohol evaporated in the normal pressureflash tower 12 and/or the normal pressure flash tower 22 can be used asan energy source for increasing a temperature of fat and oil and/oralcohol.

In a case where the first alcohol stripping step and/or the secondalcohol stripping step is refinement with one stage in the pressureflash tower, the amount of alcohol contained in a heavy liquid extractedfrom the bottom of the pressure flash tower is large, which may worsen aseparation efficiency in the phase-separation step that is a next step.Specifically, there is a possibility that fatty acid alkyl ester and/ormonoglyceride is distributed to the glycerin phase, and the yield andthe purity of fatty acid alkyl ester and/or glycerin drop.

In FIG. 1, the heat of the unreacted alcohol evaporated in the firsthigh pressure flash tower 11 and the second high pressure flash tower 21is used in the alcohol refining step. However, the present invention isnot limited to this. Only the heat of the unreacted alcohol evaporatedin one of the first high pressure flash tower 11 and the second highpressure flash tower 21 may be used in the alcohol refining step.

The first high pressure flash tower 11, the second high pressure flashtower 21, the first low pressure flash tower 12, and the second lowpressure flash tower 22 may be conventional and well known flash towers.

(Detail of the Alcohol Refining Step)

The following details the alcohol refining step. The alcohol refiningstep is carried out in the alcohol refining tower 13. The alcoholrefining step is a step of refining unreacted alcohol into alcohol thatcan be reused as a raw material for the first and second reaction steps.“Refining” in the present specification etc. means a refining unreactedalcohol into alcohol that can be used as a raw material in the reactionstep.

To be more specific, the alcohol refining tower 13 used in the alcoholrefining step is provided with the heat exchangers 30 and 31 at itsbottom, and evaporates the unreacted alcohol with use of energyrecovered in the heat exchangers 30 and 31 so as to obtain a refinedalcohol.

Contaminants contained in the unreacted alcohol are mainly water. In acase where the alcohol to be refined has a boiling water lower than thatof water, the refined alcohol is obtained as gas from the upper part ofthe alcohol refining tower 13, and wastes having a boiling point higherthan the alcohol, such as water, are extracted from the lower part ofthe alcohol refining tower 13 and are supplied to the waste storage tank4. In a case where the alcohol to be refined has a boiling point higherthan that of water, the refined alcohol is extracted from the lower partof the alcohol refining tower 13 and wastes having a boiling point lowerthan that of the alcohol are exhausted as gas from the upper part of thealcohol refining tower 13.

In a case where the alcohol obtained by refinement in the alcoholrefining step is reused as a raw material, concentration of waterincluded in the alcohol is preferably not more than 1000 ppm, morepreferably not more than 700 ppm, and further preferably not more than500 ppm. This is because water contained in the alcohol causeshydrolysis of fatty acid alkyl ester to proceed in the reaction step,making the yield of the fatty acid alkyl ester lower.

When the concentration of water in the alcohol is within the aboverange, it is possible to prevent decrease of catalytic ability andelution of active ingredient that are caused by fatty acid derived fromhydrolysis of fatty acid alkyl ester, so that is it possible to use acatalyst for a long time.

The heat exchangers 30 and 31 are not particularly limited. However, theheat exchangers 30 and 31 are preferably heat exchangers of a gas-liquidcontact type, since the unreacted alcohols obtained in the first andsecond alcohol stripping steps are gas. That is, it is preferable thatheat generated when condensing the unreacted alcohols obtained in thefirst and second alcohol stripping steps is recovered in the heatexchanger 30 or 31 and used as a heat source in the alcohol refiningtower 13.

To be more specific, the heat exchangers 30 and 31 cause the unreactedalcohols that are obtained as gas in the first and second alcoholstripping steps to contact with unreacted alcohol in a liquid to berefined, thereby recovering heat from the unreacted alcohols in the gasform. Subsequently, the heat recovered from the unreacted alcohols inthe gas form is used as energy for refining the unreacted alcohol in theliquid, i.e., energy used in the alcohol refining step. The unreactedalcohols from which the heat has been recovered and which have changedfrom gas to a liquid may be supplied to the alcohol refining tower 13 soas to be unreacted alcohol to be refined.

The liquid which the unreacted alcohols in the gas form is to contactwith is not limited to the unreacted alcohol in the liquid to berefined, and may be other liquid.

(Detail of the third Alcohol Stripping Step)

The third alcohol stripping step carried out in the alcohol evaporator23 is a step of removing alcohol from the second reaction liquid and thefirst glycerin phase before phase-separating the second reaction liquidand the first glycerin phase and obtaining an end product (fatty acidalkyl ester and/or glycerin).

The alcohol evaporator 23 is an evaporator provided with a heatexchanger (heater) with a short residence time. Specific examplesthereof include a thin film evaporator with an agitating rotor (e.g.wiped film evaporator), with tubes arranged as a bundle (e.g. fallingfilm evaporator, climbing film evaporator), and with a centrifugal rotor(centrifugal thin film evaporator).

The residence time is preferably within 20 minutes, and more preferablywithin 10 minutes. When the residence time is long, a reverse reactionof the transesterification occurs depending on a temperature of aheater, which decreases the yield of fatty acid alkyl ester, accompaniedby decrease in purity of a refined product.

The temperature of the heater in the third alcohol stripping step ispreferably not more than 250° C., and more preferably not more than 200°C. When the temperature of the heater exceeds 250° C., the reversereaction of the transesterification occurs within an extremely shorttime, which is not preferable. For example, a time necessary for 0.1 mol% of fatty acid alkyl ester to decompose due to the reverse reaction is35 minutes at 150° C., 10 minutes at 200° C., and 4 minutes at 250° C.

The pressure in the third alcohol stripping step ranges preferably from0.012 to 0.090 MPa, more preferably from 0.020 to 0.050 MPa. When thepressure is within the above range, evaporation can be performed at atemperature where the reverse reaction of the transesterification hardlyoccurs, and it is unnecessary to provide a cooling device for condensingalcohol.

In the third alcohol stripping step, by using the alcohol evaporator 23with the above arrangement, it is possible to sufficiently evaporate andremove a small amount of alcohols from the second reaction liquid andthe first glycerin phase without subjecting the second reaction liquidand the first glycerin phase to excessive heat history. Consequently, itis possible to prevent a phenomenon that fatty acid alkyl ester and/orglycerin that is to be an end product is heated excessively and areverse reaction proceeds. Further, since the unreacted alcohol issufficiently removed before the second phase-separation step, it ispossible to prevent a phenomenon that fatty acid alkyl ester isdistributed to the second glycerin phase in the second phase-separationstep and the yield of fatty acid alkyl ester drops. Further, since it ispossible to reduce the amount of alcohol in the second fatty acid alkylester phase and the second glycerin phase that are obtained in thesecond phase-separation step, it is unnecessary to perform refinementafter the second phase-separation step.

As described above, in the method of the present embodiment forproducing fatty acid alkyl ester and/or glycerin, the unreacted alcoholin the second reaction liquid is evaporated in the second alcoholstripping step. Further, the first glycerin phase is obtained byphase-separating the first reaction liquid from which the unreactedalcohol has been evaporated in the first alcohol stripping step.Consequently, the second reaction liquid and the first glycerin phasefrom both of which alcohol is to be removed in the third alcoholstripping step have small amount of unreacted alcohol. Therefore, in thethird alcohol stripping step, it is only necessary to evaporate andremove a small amount of alcohol contained in the second reaction liquidand the first glycerin phase. This allows further reducing the alcoholcontent in a resulting refined product.

Specifically, in the third alcohol stripping step, refinement isperformed so that the alcohol content in the resulting refined productis more preferably not more than 0.5 wt %, still more preferably notmore than 0.3 wt %, and further more preferably not more than 0.2 wt %.

As described above, in the present embodiment, the alcohol content inthe refined product is very low, so that it is possible to increase theyield of fatty acid alkyl ester and to omit a refinement process afterthe second phase-separation step.

In the present embodiment, the first glycerin phase is evaporated in thealcohol evaporator 23. However, the present invention is not limited tothis, and the first glycerin phase may be evaporated in otherevaporator. However, in that case, there is a possibility that unreactedalcohol is not sufficiently evaporated from the first glycerin phase.Further, in a case where an already existing alcohol evaporator is notused, additional costs may be required. However, even in such a case,the present invention is designed so that at least the second reactionliquid is evaporated in the evaporator, and therefore the presentinvention yields the above effect.

(First Phase Separator 14 and Second Phase Separator 24)

The first phase separator 14 and the second phase separator 24 may becontinuous gravity settlers, but are preferably coalescers, or arecombination of them. A coalescer is a device for separating a mixture ofimmiscible liquids, wherein the mixture comprises a discontinuous liquidphase that is dispersed in a continuous liquid phase, by contacted witha coalescing medium to cause the dispersed phase to merge into largerdroplets which then separate from the continuous phase on the basis ofdensity. This allows very swift phase-separation between an upper phaseand a lower phase with sureness. Consequently, it is possible to obtainboth the upper phase and the lower phase with high purity in a shorttime.

A transesterification between fat and oil and alcohol is an equilibriumreaction. Consequently, when glycerin is dispersed or finely dispersedin the upper phase (fatty acid alkyl ester phase) that has beenphase-separated in the first phase separator 14, a reaction in thesecond reaction step is disadvantageous in terms of equilibrium, andtherefore unconverted glycerides are likely to remain.

The first phase separator 14 performs phase-separation with use of acoalescer, thereby preventing glycerin from being dispersed or finelydispersed in the upper phase. This increases the yield of fatty acidalkyl ester that is an end product.

In the reaction for generating fatty acid alkyl ester and glycerin inthe present embodiment, there is a case where water is produced as aby-product in the reaction step. When water produced as a by-product inthe first reaction step is supplied along with the upper phase (fattyacid alkyl ester phase) to the second reactor 20 in the second reactionstep that is a subsequent stage, the water may cause deterioration of asolid catalyst and by-production of free fatty acid. However, since thewater is distributed to the lower phase (glycerin phase) in thephase-separation step, the deterioration of the solid catalyst and theby-production of the free fatty acid do not occur when the upper phaseand the lower phase are surely phase-separated.

Therefore, when the first phase separator 14 performs phase-separationwith use of a coalescer, it is possible to increase the yield of fattyacid alkyl ester that is an end product, and to lengthen the life of thesolid catalyst in the second reactor 20.

(Addition)

In order to obtain fatty acid alkyl ester and/or glycerin each withfurther higher purity in the first phase separator 14 and the secondphase separator 24, there may be additionally provided a refining towerin a stage subsequent to the first phase separator 14 and the secondphase separator 24.

A part of heat obtained in the first alcohol stripping step or thesecond alcohol stripping step may be used as an energy source in thealcohol evaporator 23.

(Detail of Removal Step)

An explanation is made as to the removal step with reference to FIG. 2.FIG. 2 is a block diagram schematically illustrating a productiondevice.

As illustrated in FIG. 2, a production device 1 for producing fatty acidalkyl ester and/or glycerin includes an alcohol storage tank 2, a fatand oil storage tank 3, a packed device 25, a reactor 26, an alcoholstripping tower 27, an alcohol refining tower 28, a solid-liquidseparator 29, and a phase separator 32. The reactor 26 corresponds tothe first reactor 10 in FIG. 1, the alcohol stripping tower 27corresponds to the first high pressure flash tower 11 and the first lowpressure flash tower 12 in FIG. 1, the alcohol refining tower 28corresponds to the alcohol refining tower 13 in FIG. 1, and the phaseseparator 32 corresponds to the first phase separator 14 in FIG. 1.

The alcohol storage tank 2 is a tank in which alcohols are stored, andthe fat and oil storage tank 3 is a tank in which fats and oils arestored. The alcohol storage tank 2 and the fat and oil storage tank 3are connected with lines 50 and 51, respectively, and the lines 50 and51 are connected with a line 52 that is connected with the upper side ofthe reactor 26 (the end of the reactor 26 to which end a reactionmaterial is supplied). That is, the alcohol storage tank 2 is connectedwith the line 52 via the line 50, and the fat and oil storage tank 3 isconnected with the line 52 via the line 51.

The line 52 is provided with the packed device 25, and a mixture ofalcohols and fats and oils is supplied to the reactor 26 via the packeddevice 25. The reactor 26 is connected with the alcohol stripping tower27 via the line 53, the alcohol stripping tower 27 is connected with thealcohol refining tower 28 via the line 54, and the alcohol strippingtower 27 is connected with the phase separator 32 via the line 56. Theline 56 is provided with the solid-liquid separator 29, and a reactionliquid from the alcohol stripping tower 27 is supplied to the phaseseparator 32 via the solid-liquid separator 29.

The alcohol refining tower 28 is connected with the alcohol storage tank2 via the line 55. Alcohol collected in the alcohol refining tower 28goes back to the alcohol storage tank 2 via the line 55 and is reused asa reaction material.

The removal step is a step of removing at least one of phosphorous,phosphorous compounds, calcium, and calcium compounds from a reactionmaterial including fats and oils and alcohols through an adsorptionprocess. That is, the removal step is a step of reducing phosphorous,phosphorous compounds, calcium, or calcium compounds that is included inthe reaction material.

As illustrated in FIG. 2, the removal step is performed in the packeddevice 25 connected with the alcohol storage tank 2 and the fat and oilstorage tank 3 via the lines 50 and 51, respectively.

The packed device 25 has a hollow shape, and is filled with an adsorberthat adsorbs at least one of phosphorous, phosphorous compounds,calcium, and calcium compounds. Consequently, phosphorous, calcium andcompounds thereof contained in a mixture liquid including the fat andoil and the alcohol that is introduced into the packed device 25 areremoved by the adsorber that fills the packed device 25. The adsorberthat fills the packed device 25 is not particularly limited as long asthe adsorber adsorbs at least one of phosphorous, phosphorous compounds,calcium, and calcium compounds. Specific examples of the adsorberinclude silica, alumina, silica-alumina, activated clay, diatomite,titania, zirconia, iron oxide, hydrotalcite, and activated carbon. Amongthem, silica, alumina, silica-alumina, titania, zirconia, and activatedcarbon are more preferable.

In the present specification etc., concentration of phosphorous atoms(which may be also referred to as “phosphorous concentration”hereinafter) and concentration of calcium atoms (which may be alsoreferred to as “calcium concentration” hereinafter) are obtained throughan Inductively Coupled Plasma Mass Spectrometer (ICP-MS).

In the removal step, phosphorous concentration in the reaction materialincluding the fat and oil and the alcohol is preferably less than 2.5ppm, more preferably less than 2 ppm, and still more preferably lessthan 1.5 ppm. Further, calcium concentration in the reaction materialincluding the fat and oil and the alcohol is preferably less than 1 ppm,more preferably less than 0.8 ppm, and still more preferably less than0.5 ppm, and most preferably less than 0.2 ppm. When the phosphorousconcentration is at least less than 2.5 ppm and the calciumconcentration is at least less than 1 ppm in the reaction materialincluding the fat and oil and the alcohol, it is possible to reduce theamount of the surface of the solid catalyst covered by at least one ofphosphorous, phosphorous compounds, calcium, and calcium compounds inthe later reaction step. This allows slowing decrease in activity of thesolid catalyst due to covering by at least one of phosphorous,phosphorous compounds, calcium, and calcium compounds. That is, thisallows lengthening the life of the solid catalyst.

Further, when the life of the solid catalyst is lengthened, frequency ofcatalyst exchange is decreased, and labor required for catalyst exchangecan be reduced. Further, since it is possible to increase the amount offatty acid alkyl ester and/or glycerin produced with respect to the sameamount of the solid catalyst, it is possible to reduce costs for thesolid catalyst with respect to each product, which allows increasingproductivity of fatty acid alkyl ester and/or glycerin.

In FIG. 2, the packed device 25 is positioned at a point after the lines50 and 51 have joined. However, the position of the packed device 25 isnot limited to this as long as the packed device 25 is positioned at apoint before the transesterification. That is, the packed device 25 maybe positioned on the lines 50 and 51, may be positioned at an entranceof the reactor 26 (supply port for the reaction material) as explainedbelow, or may be positioned to be integral with the fat and oil storagetank 2 and the alcohol storage tank 3. Further, the packed device 25 maybe positioned at a point before the fat and oil storage tank 2 and thealcohol storage tank 3 so that the fat and oil and the alcohol aresupplied to respective storage tanks while meeting at least one of twoconditions, i.e., a condition that the total of phosphorousconcentration is less than 2.5 ppm in the reaction and a condition thatthe total of calcium concentration is less than 1 ppm in the reaction.

As described above, the amounts of phosphorous, phosphorous compounds,calcium, and calcium compounds are so little that they may be ignored.Therefore, the present invention may be arranged so that only thephosphorous concentration and the calcium concentration in the fat andoil are reduced in order that the phosphorous concentration and thecalcium concentration in the reaction material including the fat and oiland the alcohol are less than 2.5 ppm and less than 1 ppm, respectively.

Further, it is preferable that a plurality of the packed devices 25 arearrayed in parallel with respect to a direction in which the material issupplied. Consequently, while an adsorber in one packed device isreplaced, it is possible to remove at least one of phosphorous,phosphorous compounds, calcium, and calcium compounds with use of otherpacked device that is not replaced. This allows replacement of anadsorber in the packed device without stopping an operation of theproduction device, i.e., without stopping production of fatty acid alkylester and/or glycerin. This prevents deterioration in productivity offatty acid alkyl ester and/or glycerin.

The removal of at least one of phosphorous, phosphorous compounds,calcium, and calcium compounds is not necessarily performed by thepacked device 25 as long as at least one of phosphorous, phosphorouscompounds, calcium, and calcium compounds in a reaction material for antransesterification can be removed. A device having other removal meanssuch as film separation, evaporation, and extraction may be providedinstead of the packed device 25 and the removal may be performed by thedevice.

Before the removal step, fat and oil that are raw materials aresubjected to a degumming process in which a gum component included inthe fat and oil, such as phospholipid and protein, is removed. Thedegumming process is a conventional and well-known process.Specifically, the degumming process is a step of adding phosphoric acid,sulfuric acid, hydrochloric acid, boric acid or citric acid and water tofat and oil and a hydrated gum component is removed by centrifugalseparation.

(Solid-Liquid Separation Step)

The following explains the solid-liquid separation step in thesolid-liquid separator 29 in FIG. 2. The solid-liquid separation step isa step of removing a solid material mainly made of sterols from thereaction liquid obtained in the reaction step or from the reactionliquid which has been subjected to the alcohol stripping step andconsequently has reduced unreacted alcohol. In the presentspecification, a sterol indicates alcohol with a steroid skeleton thatis known to exist as a minor constituent in animal/plant oil etc., andan ester compounds thereof. Further, here, removal of a solid materialindicates not only complete removal of the solid material in thereaction liquid, but also removal of at least part of the solidmaterial.

The solid-liquid separation step is carried out in such a manner thatthe reaction liquid obtained in the reaction step or the reaction liquidwhich has been subjected to the alcohol stripping step and consequentlyhas reduced unreacted alcohol is caused to pass through a solid-liquidseparator. The solid-liquid separator 29 is not particularly limited aslong as it can remove sterols deposited in the reaction liquid. Forexample, a filter, a centrifugal separator, a sedimentation tank etc.may be used. Among them, a filter is preferable in terms of energyefficiency and the scale of a device. Examples of the filtration typeinclude: a media filtration such as a screen filtration (e.g. membranefiltration and microstrainer), a deep bed filtration (e.g. particle bedfiltration and fiber bed filtration); a cake filtration such as vacuumfiltration, a pressure filtration (drum type, disc type, horizontaltype, leaf type, candle type etc.), a filter press, a roll (belt) press,and a screw press. Among them, the media filtration is preferable interms of concentration of a solid material in the reaction liquid,particle size, device costs and running costs. Filtration rating of thefilter is not particularly limited as long as it can remove solidmaterials to such an extend that the effect of the solid-liquidseparation step is yielded. In terms of particle size of the solidmaterials, the filtration rating is preferably not more than 100 μm,more preferably not more than 50 μm, and still more preferably not morethan 10 μm, and most preferably not more than 5 μm. Further, in order toassure a sufficient flow of a liquid, the lower limit of the filtrationrating is preferably not less than 0.1 μm, and more preferably not lessthan 1 μm. In the present specification, “filtration rating” indicatesan ability of a filter that can collect not less than 99.9% of a solidmaterial with a minor axis equal to or larger than the value of thefiltration rating. That is, a filter whose filtration rating is 5 μm canremove not less than 99.9% of a solid material with a minor axis equalto or larger than 5 μm that is included in a reaction liquid supplied tothe solid-liquid separation step.

It is preferable that the solid-liquid separation step is carried outafter the separation step. In the separation step, along with separationof the unreacted alcohol from the reaction liquid, solubility of sterolsin the reaction liquid drops, making solid sterols more likely todeposit. For that reason, when the solid-liquid separation step iscarried out after the separation step, it is possible to satisfactorilyremove solid sterols. Further, solubility of sterols depends on atemperature. In order to remove sterols more effectively, thesolid-liquid separation step is carried out preferably at 100° C. orless, more preferably at 80° C. or less, and still more preferably at60° C. or less. The lower limit of the temperature is preferably 30° C.or more, and more preferably 40° C. or more, in order to carry out thesolid-liquid separation step at a temperature where intermediateglycerides in the reaction liquid do not deposit.

In the present embodiment, an explanation was made as to a case whereone solid-liquid separator 29 is provided between the reactor 26 and thephase separator 32. However, the present invention is not limited tothis case. For example, a plurality of solid-liquid separators 29 may beprovided. The plurality of solid-liquid separators 29 may be provided atthe same position on a flow path of the reaction liquid, or may beprovided at different positions, respectively. Further, when a pluralityof filters are provided at the same position, it is preferable that thefilters are positioned in parallel with respect to a flow of thereaction liquid. This positioning is advantageous in that when one ofthe filters drops its filtering ability, by controlling the flow of thereaction liquid so that the reaction liquid flows to the other filter,it is possible to avoid complete stopping of the operation of theproduction device. Therefore, the present embodiment can provide aproduction device with higher operation efficiency.

(Solid Catalyst, Alcohol, and Fat and Oil)

An explanation is made as to a solid catalyst, alcohol, and fat and oilthat can be preferably employed in the present invention.

(Solid Catalyst)

It is preferable that a solid catalyst preferably used in the presentinvention is a catalytic compound that hardly dissolves in a reactionliquid containing raw materials and products in a transesterification,and is a solid catalyst having insolubility with respect to a reactionliquid containing fat and oil and alcohol as raw materials and fattyacid alkyl ester and glycerin as products. “Insolubility” of the solidcatalyst of the present specification etc. indicates that an activeingredient (e.g., active metal ingredient) is 1000 ppm or less,preferably 800 ppm or less, more preferably 600 ppm or less, still morepreferably 300 ppm or less, and most preferably not detected by ananalyzer. Concentration (elution amount) of the active ingredient of theinsoluble solid catalyst in the reaction liquid can be measured throughX-ray Fluorescence Analysis (XRF). In the X-ray Fluorescence Analysis,it is possible to use a reaction liquid after reaction without changinga liquid state thereof. In a case of measuring a minuter elution amount,the measurement may be performed through Inductively Coupled PlasmaOptical Emission Spectrometry (ICP-OES).

It is preferable that the solid catalyst preferably used in the presentinvention can be easily removed from the reaction system after thetransesterification between the fat and oil and the alcohol. Further, itis preferable that the solid catalyst is a catalyst having activity withrespect to an esterification reaction of free fatty acid contained inthe fat and oil, i.e., a catalyst having activity with respect to bothof a transesterification of glyceride contained in the fat and oil andan esterification reaction of free fatty acid contained in the fat andoil. This allows simultaneously performing the transesterification andthe esterification reaction even when the fat and oil that are rawmaterials contain free fatty acid. This allows increasing the yield offatty acid alkyl ester without separately performing esterificationreaction and the transesterification.

Specific examples of the solid catalyst preferably used in the presentinvention include alkali metal compound, alkali earth metal compound,aluminum-containing compound, silicon-containing compound,titanium-containing compound, vanadium-containing compound,chrome-containing compound, manganese-containing compound,iron-containing compound, cobalt-containing compound, nickel-containingcompound, copper-containing compound, zinc-containing compound,zirconium-containing compound, niobium-containing compound,molybdenum-containing compound, tin-containing compound, rareearth-containing compound, tungsten-containing compound, lead-containingcompound, bismuth-containing compound, and ion exchange resin.

The above compound is not particularly limited as long as it containsthe above essential component. Preferable examples of the form of thecompound include single oxide, mixed oxide, complex oxide, hydrosulfate,phosphate, cyanide, halide, and complex. Among them, single oxide, mixedoxide, complex oxide, and cyanide are more preferable. Specific examplesinclude aluminum oxide, titanium oxide, manganese oxide, zinc oxide,zirconium oxide, mixed and/or complex oxide among these oxides orbetween these oxides and other metals, zinc cyanide, iron cyanide,cobalt cyanide, mixed and/or complex cyanide among these cyanides orbetween these cyanides and other metals. These may be supported by asupporter or be fixed on the supporter. Examples of the supporterinclude silica, alumina, silica-alumina, zeolite, activated carbon,diatomite, zirconium oxide, titanium oxide, tin oxide, and lead oxide.

An example of the ion exchange resin is anion exchange resin etc.Specific examples of the anion exchange resin include strong base anionresin and weak base anion resin. When anion exchange resin is classifiedin terms of the degree of crosslinking or porosity, the anion exchangeresin may be of gel type, porous type, high-porous type etc.

(Fat and Oil)

Fat and oil preferably used in the present invention are notparticularly limited as long as they contain an ester between fatty acidand glycerin, serve as raw materials for fatty acid alkyl ester and/orglycerin in combination with alcohol, and contain an ester between fattyacid and glycerin that is so-called “fat and oil.” Normally, it ispreferable to use fat and oil that contain triglyceride (triester ofglycerin and higher fatty acid) as a main component and contains smallamounts of sub components such as diglyceride, monoglyceride, free fattyacid etc. Alternatively, fat and oil such as triolein and tripalmitinmay be used.

Specific examples of such fat and oil include: plant fats and oils suchas coconut oil, coleseed oil, sesame oil, soy bean oil, corn oil,sunflower oil, palm oil, palm kernel oil, safflower oil, linseed oil,cotton seed oil, tung oil, and castor oil; animal fats and oils such asbeef tallow, lard, fish oil, and whale oil; and used edible oils (wastededible oils). These fats and oils may be used singularly or two or moreof them may be used in combination.

In a case where the fats and oils contain impurities such asphospholipid and protein, it is preferable to add mineral acid such assulfuric acid, nitric acid, phosphoric acid, and boric acid in order toremove the impurities. In the method of the present invention forproducing fatty acid alkyl ester and/or glycerin, it is more preferableto use a catalyst whose catalysis is less likely to be prevented bymineral acid since the catalyst allows effectively producing fatty acidalkyl ester and/or glycerin even when fat and oil contain mineral acid.

(Alcohol)

In a case of targeting the production of biodiesel, alcohol preferablyused in the present invention is preferably alcohol having 1-6 carbonatoms, and more preferably alcohol having 1-3 carbon atoms. Examples ofthe alcohol having 1-6 carbon atoms include methanol, ethanol, propanol,isopropyl alcohol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol,3-pentanol, 1-hexanol, and 2-hexanol. Among them, methanol or ethanol ispreferable. These alcohols may be used singularly or two or more of themmay be used in combination.

In the method of the present invention for producing fatty acid alkylester and/or glycerin, a minor constituent other than the fat and oil,the alcohol, and the solid catalyst may exist.

“Alcohol” in the present specification etc. is a general term indicativeof a component in which hydrogen atoms of carbon hydrogen are replacedwith hydroxyl groups.

The present invention is not limited to the description of theembodiments above, but may be altered by a skilled person within thescope of the claims. An embodiment based on a proper combination oftechnical means disclosed in different embodiments is encompassed in thetechnical scope of the present invention.

The following further details the present invention with reference toExamples. The present invention is not limited to these Examples and maybe altered in minor parts.

Examples Example 1

In the present Example, palm oil (fat and oil) and methanol (alcohol)were used as reaction materials. The palm oil used here was degummedpalm oil obtained by adding phosphoric acid and thus precipitating andremoving protein and phospholipid included in the palm oil beforehand.The ratio of free fatty acid contained in the used palm oil was 5.1 wt %and the moisture content was 0.06 wt %.

The yields of produced fatty acid methyl ester (fatty acid alkyl ester)and glycerin were calculated as follows.

Yield of fatty acid methyl ester=(mol number of fatty acid alkyl esterin upper phase (ester phase) extracted from the second phase separator24 )/(mol number of triglyceride×3+mol number of diglyceride×2+molnumber of monoglyceride each at entrance of the first reactor 10).

Yield of glycerin=(mol number of glycerin in lower phase (glycerinphase) extracted from the second phase separator 24 )/(sum of molnumbers of glycerides at entrance of the first reactor 10)

(Preparation of Catalyst)

The following explains the catalyst used in the present Example.Manganese carbonate (30 parts), anatase titanium oxide (19 parts), andalkyl cellulose (1 part; metolose 90SH-15000 manufactured by Shin-EtsuChemical Co., Ltd.) were mixed sufficiently. 19 parts of water was addedevenly to the mixed powders in several numbers and the mixture wasfurther mixed and then extruded out of a hole of 0.4 mm in diameter by awet-type extrusion granulator (Dome Gran DG-L1 manufactured by FujiPaudal co., ltd). The extruded mixture was dried at 120° C. for one dayand one night, sheared by a fine pulverizer (sample mill manufactured byFuji Paudal co., ltd) to have a length of approximately 5 mm, and bakedat 1000° C. for 5 hours in the air atmosphere. Thus, catalyst MnTiO3 wasobtained.

(Production of Fatty Acid Alkyl Ester and Glycerin)

Fatty acid alkyl ester and glycerin were produced with use of theproduction device illustrated in FIG. 1. The method for the productionis specifically explained below. Palm oil (2.5 kg/h) and methanol (2.5kg/h) were continuously flowed with use of a constant flow pump andtheir temperatures and their pressures were increased up to 200° C. and5 MPa, respectively, by a heat exchanger. These liquids were mixed witheach other by a mixer and the mixture was continuously flowed downwardfrom the upper part of the first reactor 10. The material balance beforeand after the reaction was shown in Table 1. The reaction liquidobtained in the first reactor 10 was supplied to the first high pressureflash tower 11. The pressure of the first high pressure flash tower 11was 0.35 MPa. Then, a heavy liquid continuously extracted from thebottom of the first high pressure flash tower 11 was supplied to thefirst low pressure flash tower 12.

Unreacted methanol (1.72 kg/h) continuously extracted from the top ofthe first high pressure flash tower 11 was supplied to the heatexchanger 30 and heat of the unreacted methanol was recovered with theheat exchanger 30 and then the unreacted alcohol was supplied to thealcohol refining tower 13.

Unreacted methanol (0.25 kg/h) continuously extracted from the top ofthe first low pressure flash tower 12 was supplied to the heat exchangerfor increasing the temperature of methanol used in the first reactionstep and heat of the unreacted methanol was recovered in the heatexchanger and then the unreacted methanol was supplied to the alcoholrefining tower 13.

The heavy liquid extracted from the bottom of the first low pressureflash tower 12 was supplied to the heat exchanger for increasing thetemperature of palm oil used in the first reaction step and heat of theheavy liquid was recovered in the heat exchanger and then the heavyliquid was supplied to the first phase separator 14 and subjected tophase-separation. The upper phase (fatty acid alkyl ester phase)extracted from the first phase separator 14 included 87.1% of fatty acidmethyl ester, 2.4% of triglyceride, 1.1% of diglyceride, 3.5% ofmonoglyceride, and 5.4% of methanol. The lower phase (glycerin phase)included 58.2% of glycerin, 0.3% of fatty acid methyl ester, 0.4% ofmonoglyceride, and 41.1% of methanol.

Subsequently, the upper phase (fatty acid alkyl ester phase) (2.67 kg/h)extracted from the first phase separator 14 and methanol (2.36 kg/h)were heated up to 200° C. and pressured to 5 MPa by a heat exchanger.These liquids were mixed with each other by a mixer, and continuouslyflowed downward from the upper part of the second reactor 20. Table 1shows the material balance before and after the reaction.

The reaction liquid obtained in the second reactor 20 was supplied tothe second high pressure flash tower 21. The pressure of the second highpressure flash tower 21 was 0.35 MPa. Then, the heavy liquidcontinuously extracted from the bottom of the second high pressure flashtower 21 was supplied to the second low pressure flash tower 22.

Unreacted methanol (1.85 kg/h) continuously extracted from the top ofthe second high pressure flash tower 21 was supplied to the heatexchanger 31 and heat of the unreacted methanol was recovered in theheat exchanger 31. Further, the unreacted methanol was supplied to theheat exchanger for increasing the temperature of methanol used in thesecond reaction step and heat of the unreacted methanol was recovered inthe heat exchanger and then supplied to the alcohol storage tank 3.

Next, the heavy liquid extracted from the bottom of the second lowpressure flash tower 22 and the lower phase (glycerin phase) extractedfrom the first phase separator 14 were mixed with each other and themixture was supplied to the alcohol evaporator 23. The alcoholevaporator 23 was a thin film evaporator. The pressure here was 0.034MPa and the temperature of a heater was 175° C. The unreacted methanolextracted from the top of the alcohol evaporator 23 was supplied to thealcohol refining tower 13.

The heavy liquid extracted from the bottom of the alcohol evaporator 23was supplied to the heat exchanger for increasing the temperature of thereaction liquid used in the second reaction step (i.e., the upper phaseextracted from the first phase separator 14) and heat of the heavyliquid was recovered in the heat exchanger and then the heavy liquid wassupplied to the second phase separator 24 and subjected tophase-separation. The upper phase (fatty acid alkyl ester phase)extracted from the second phase separator 24 included 99.4% of fattyacid alkyl ester, 0.10% of triglyceride, 0.06% of diglyceride, 0.41% ofmonoglyceride, and 0.05% of methanol. The lower phase (glycerin phase)included 99.7% of glycerin and 0.3% of methanol.

In Example 1, the yield of fatty acid alkyl ester was 99.5% and theyield of glycerin was 98.9%.

Subsequently, in the alcohol refining tower 13, methanol was refinedfrom unreacted methanol extracted from the tops of the first pressureflash tower 11, the first low pressure flash tower 12, and the alcoholevaporator 23. In the present Example, the alcohol refining tower 13 wasa distillation column whose number of plates was 15, the reflux ratiothereof was 0.25, the bottom operation temperature was 74° C., and theoperation pressure was a normal pressure. All the amount of heatrequired in the alcohol refining tower 13 was compensated by thequantity of heat of the unreacted methanol extracted from the tops ofthe first high pressure flash tower 11 and the second high pressureflash tower 21. Methanol whose water content was 200 ppm was obtainedfrom the top of the alcohol refining tower 13 and was reused as areaction material. Table 2 shows the amount of heat required in eachstep.

TABLE 1 Second Second Flow amount First reactor First reactor reactorreactor (kg/hr) entrance exit entrance exit Triglyceride 2.420 0.0640.064 0.002 Diglyceride 0.077 0.031 0.031 0.001 Monoglyceride 0.0030.106 0.106 0.010 Fatty acid 0.000 2.325 2.325 2.494 Ester Glycerin0.000 0.226 0.013 0.048 Methanol 2.500 2.249 2.500 2.482 Sum 5.000 5.0005.039 5.039

TABLE 2 Quantity of heat (kJ) Ex 1 and 2 Com Ex 1 Ex 3 Increase intemperature and 2400 2900 2700 pressure in first reaction step Increasein temperature and 1700 2800 1900 pressure in second reaction stepAlcohol evaporation step 1000 1000 1200 (Alcohol evaporator 23) Alcoholrefining step 0 2700 0 (Alcohol refining tower 13) Sum 5100 10400 5800

Comparative Example 1

There was performed the same operation as Example 1 except that the heatwas not recovered in Comparative Example 1. The amount of heat requiredin each step is shown in Table 2.

Example 2

Heat of unreacted methanol continuously extracted from the tops of thefirst high pressure flash tower 11 and the first low pressure flashtower 12 was recovered in the same operation as Example 1 and then theunreacted methanol was supplied to the alcohol storage tank 3.

Further, Heat of unreacted methanol continuously extracted from the topsof the second high pressure flash tower 21 and the second low pressureflash tower 22 was recovered in the same operation as Example 1 and thenthe unreacted methanol was supplied to the alcohol refining tower 13.

Fatty acid methyl ester and glycerin were produced in the same manner asExample 1 except for the above operations. In Example 2, the refluxratio of the alcohol refining tower 13 was 0.16, the bottom operationtemperature was 80° C., and the operation pressure was a normalpressure.

In Example 2, all the amount of heat required in the alcohol refiningtower 13 could be compensated by the amount of heat of unreactedmethanol extracted from the tops of the first high pressure flash tower11 and the second high pressure flash tower 21. Further, methanol whosewater content was 470 ppm was obtained from the top of the alcoholrefining tower 13, and the methanol could be reused as a reactionmaterial.

Example 3

Without using the first high pressure flash tower 11, the heavy liquidextracted from the bottom of the first low pressure flash tower 12 wassupplied to the first phase separator 14. The pressure here was 0.25MPa.

Further, without using the second low pressure flash tower 22, the heavyliquid extracted from the bottom of the second high pressure flash tower21 was supplied to the alcohol evaporator 23. The pressure here was 0.25MPa.

Further, unreacted methanol extracted from the tops of the firstpressure flash tower 11 and the alcohol evaporator 23 was supplied tothe alcohol refining tower 13.

Fatty acid methyl ester and glycerin were produced in the same manner asExample 1 except for the above operations. In Example 3, the refluxratio of the alcohol refining tower 13 was 0.29, the bottom operationtemperature was 83° C., and the operation pressure was a normalpressure.

In Example 3, the purity of fatty acid methyl ester was 99.3%. Inaddition, 0.90% of triglyceride, 0.06% of diglyceride, 0.50% ofmonoglyceride, and 0.05% of methanol were contained.

In Example 3, all the amount of heat required in the alcohol refiningtower 13 could be compensated by the amount of heat of the unreactedmethanol extracted from the tops of the first high pressure flash tower11 and the second high pressure flash tower 21. Further, methanol whosewater content was 370 ppm was obtained from the top of the alcoholrefining tower 13, and the methanol could be reused as a reactionmaterial. The amount of heat required in each step is shown in Table 2.

Comparative Example 2

Without using the first high pressure flash tower 11, the heavy liquidextracted from the bottom of the first low pressure flash tower 12 wassupplied to the first phase separator 14.

Further, without using the second high pressure flash tower 21, thereaction liquid obtained in the second reactor 20 was supplied to thesecond low pressure flash tower 22. Unreacted methanols continuouslyextracted from the tops of the first low pressure flash tower 12 and thesecond low pressure flash tower 22 were supplied to the heat exchangersand 31, respectively, and the heat of the unreacted methanols wasrecovered.

Further, unreacted methanols extracted from the tops of the first normalpressure flash tower 12 and the alcohol evaporator 23 were supplied tothe alcohol refining tower 13.

Fatty acid methyl ester and glycerin were produced in the same manner asExample 1 except for the above operations.

The condensation temperature of unreacted methanols continuouslyextracted from the tops of the first low pressure flash tower 12 and thesecond low pressure flash tower 22 was 64° C., and the bottomtemperature of the alcohol refining tower 13 increased only up to 54° C.That is, it was impossible to refine alcohol in the alcohol refiningtower 13.

Example 4

In the present example, palm oil and methanol were used as reactionmaterials. The palm oil was degummed palm oil obtained by addingphosphoric acid and thus precipitating and removing protein andphospholipid. The percentage of free fatty acid contained in the palmoil was 5.1 wt % and the percentage of moisture content contained in thepalm oil was 0.06 wt %.

The yields of fatty acid alkyl ester and glycerin were calculated withuse of equations that are the same as those in Example 1. The solidcatalyst used here was MnTiO3 catalyst.

Fatty acid alkyl ester and glycerin were produced with use of theproduction device 1 as illustrated in FIG. 1. Palm oil (2.5 kg/h) andmethanol (2.5 kg/h) were mixed with each other by a constant flow pumpand was continuously flowed downward from the upper part of the firstreactor 10. The pressure in the reactor was 5 MPa and the temperature inthe reactor was 200° C. The material balance before and after thereaction is shown in Table 3.

TABLE 3 Second Second Flow amount First reactor First reactor reactorreactor (kg/hr) entrance exit entrance exit Triglyceride 2.420 0.0640.064 0.002 Diglyceride 0.077 0.031 0.031 0.001 Monoglyceride 0.0030.106 0.106 0.010 Fatty acid 0.000 2.325 2.325 2.494 ester Glycerin0.000 0.226 0.013 0.048 MeOH 2.500 2.249 2.500 2.482 Sum 5.000 5.0005.039 5.039

The reaction liquid obtained in the first reactor 10 was supplied to thefirst high pressure flash tower 11. The pressure of the first highpressure flash tower 11 was 0.35 MPa. The heavy liquid continuouslyextracted from the bottom of the first high pressure flash towerincluded 16.6 % of methanol. The heavy liquid was supplied to the firstlow pressure flash tower 12. The heavy liquid extracted from the bottomof the first low pressure flash tower 12 included 9.7% of methanol.

The heavy liquid extracted from the bottom of the first low pressureflash tower 12 was supplied to the separator 14 and was subjected tophase-separation. The upper phase (fatty acid alkyl ester phase)extracted from the separator 14 contained 87.1% of fatty acid methylester, 2.4% of triglyceride, 1.1% of diglyceride, and 3.5% ofmonoglyceride, and 5.4% of methanol. The lower phase (glycerin phase)contained 58.2% of glycerin, 0.3% of fatty acid methyl ester, 0.4% ofmonoglyceride, and 41.4% of methanol. The upper phase (fatty acid alkylester phase) (2.67 kg/h) extracted from the separator 14 and methanol(2.36 kg/h) were mixed with each other and the mixture was continuouslyflowed downward from the upper part of the second reactor 20. Thepressure in the reactor was 5 MPa and the temperature in the reactor was200° C. The material balance before and after the reaction is shown inTable 3.

The reaction liquid obtained in the second reactor 20 was supplied tothe second high pressure flash tower 21. The pressure of the second highpressure flash tower 21 was 0.35 MPa. The heavy liquid continuouslyextracted from the bottom of the second high pressure flash towercontained 14.4% of methanol.

The heavy liquid extracted from the bottom of the second low pressureflash tower 22 and the lower phase (glycerin phase) extracted from theseparator 14 were mixed with each other and the mixture was supplied tothe alcohol evaporator 23. The alcohol evaporator 23 was a thinevaporator. The pressure was 0.034 MPa and the temperature of a heaterwas 175° C. The residence time of the liquid at that time was 2 minutes.The heavy liquid continuously extracted from the bottom of the alcoholevaporator 23 contained 0.07% of methanol.

The heavy liquid extracted from the bottom of the alcohol evaporator 23was supplied to the separator 24 and was subjected to phase-separation.The upper phase (fatty acid alkyl ester phase) extracted from theseparator 24 contained 99.4% of fatty acid methyl ester, 0.10% oftriglyceride, 0.06% of diglyceride, 0.41% of monoglyceride, and 0.05% ofmethanol. The lower phase (glycerin phase) contained 99.7% of glycerinand 0.3% of methanol.

The yield of fatty acid alkyl ester was 99.5% and the yield of glycerinwas 98.9%.

Comparative Example 3

There was performed the same operation as Example 4 except that methanolwas evaporated with use of an evaporator having a compulsory circulatingheat exchanger as the alcohol evaporator 23. The residence time in thealcohol refining tower 23 was 116 minutes. A reverse reaction occurredand 0.65% of fatty acid methyl ester was decomposed. The yield and thepurity of fatty acid methyl ester were 98.9% and 98.6%, respectively.The fatty acid methyl ester contained 0.32% of triglyceride, 0.18% ofdiglyceride, 0.80% of monoglyceride, and 0.12% of methanol. The yieldand the purity of glycerin were 98.1% and 99.2%, respectively.

Comparative Example 4

There was performed the same operation as Example 4 except that a liquidextracted from the bottom of the second low pressure flash tower 22 wassupplied to the separator 24, the upper phase (fatty acid alkyl esterphase) obtained in the separator 24 was evaporated by the alcoholevaporator 23, and a mixture liquid of the lower phase of the separator14 and the lower phase of the separator 24 was evaporated by a newalcohol evaporator. 0.22% of fatty acid methyl ester was distributed tothe glycerin phase in the second phase separator 24. The yield and thepurity of fatty acid methyl ester were 99.3% and 99.4%, respectively.The yield and the purity of glycerin were 98.9% and 97.7%, respectively.Glycerin contained 2.1% of fatty acid methyl ester.

Example 5

(Method for Preparing Solid Catalyst)

Manganese carbonate (239 g), anatase titanium oxide (152 g), and alkylcellulose (metolose 90SH-15000 manufactured by Shin-Etsu Chemical Co.,Ltd.) were mixed sufficiently. 150 g of water was added evenly to themixed powders in several numbers and the mixture was further mixed andthen extruded out of a hole of 0.4 mm in diameter by a wet-typeextrusion granulator (Dome Gran DG-L1 manufactured by Fuji Paudal co.,ltd). The extruded mixture was dried at 120° C. for one day and onenight, sheared by a fine pulverizer (sample mill manufactured by FujiPaudal co., ltd) to have a length of approximately 5 mm, and baked at1000° C. for 5 hours in the air atmosphere. Thus, catalyst MnTiO3 wasobtained.

An SUS-316 straight reaction tube of 10 mm in inner diameter and 210 mmin length was filled with 15 mL of the obtained solid catalyst. An exitof the reaction tube was provided with a filter and a back pressureregulator via an air-cooling tube so that the pressure could becontrolled.

(Fat and Oil and Alcohol to be Used)

Palm oil was used as fat and oil and methanol was used as alcohol. Thepalm oil was refined palm oil having been degummed.

(Production Method)

Palm oil (flow amount: 6.3 g/h) and methanol (flow amount: 6.3 g/h) weredrawn by a constant flow pump from a palm oil storage tank for storingpalm oil and a methanol storage tank for storing methanol, respectively,and are mixed with each other. The mixed palm oil and methanol wascaused to pass the SUS-316 straight-tube-packed device of 10 mm in innerdiameter and 210 mm in length that is filled with an adsorber (15 mL),and then caused to continuously flow downward from the upper part of thereaction tube. In this process, the pressures in the packed device andthe reaction tube were set to 5 MPa with use of the back pressureregulating valve. The amount of methanol supplied with respect to palmoil was 9 times larger than the theoretically required amount. Internaltemperatures of the packed device and the reaction tube were set to 200°C. by heating from the outside.

(Adsorber)

In the present Example, the adsorber was 70-180 μm spherical silica ofCARiACT Q-50 manufactured by Fuji Silysia Chemical Ltd.

(Measurement of Activity of Solid Catalyst)

Measurement of activity of MnTiO3 was performed by measuring theconversion rate of palm oil and the yield of fatty acid methyl esterwhen the reaction times were 210 hours, 402 hours, 642 hours, and 843hours. In the present example, the conversion rate of palm oil and theyield of fatty acid methyl ester were calculated in accordance with thefollowing equation.

Conversion rate of palm oil (%)=(mol number of consumed palm oil at timewhen reaction was finished)/(mol number of prepared palm oil)×100

Yield of fatty acid methyl ester (%)=(mol number of generated fatty acidmethyl ester at time when reaction was finished)/(mol number ofeffective fatty acid at time it was prepared)×100

The effective fatty acid indicates triglyceride, diglyceride,monoglyceride, and free fatty acid of fatty acid contained in the palmoil. That is, the mol number of the effective fatty acid at a time itwas prepared can be calculated in accordance with the followingequation.

Mol number of effective fatty acid at time when it was prepared(mol)=[amount of prepared palm oil (g)×saponification value of palm oil(mg (KOH)/g (palm oil))/56100]

Further, the adsorber and the catalyst that have been subjected to thereaction for 1000 hours were analyzed through X-ray FluorescenceAnalysis (XRF). The result of the analysis showed that the adsorberadsorbed 8 mg of phosphorous and phosphorous compounds and 5 mg ofcalcium and calcium compounds. On the other hand, the result of theanalysis showed that the catalyst adsorbed 25 mg of phosphorous andphosphorous compounds and 2 mg of calcium and calcium compounds.

(Measurements of Phosphorous Concentration and Calcium Concentration)

The measurements of phosphorous concentration and calcium concentrationwere performed through Inductively Coupled Plasma Mass Spectrometer(ICP-MS). Specifically, a reaction raw material to be measured (2 g) wasput in a Teflon® beaker and then subjected to thermolysis with use ofsulfuric acid, nitric acid, perchloric acid, and hydrogen peroxidesolution, and subjected to heat dissolution with use of diluted nitricacid so that the aqueous solution filled up the beaker. The obtainedaqueous solution was measured through ICP-MS so that phosphorousconcentration and calcium concentration were measured.

The result of the measurement showed that phosphorous concentration was1.5 ppm (μg/g) and calcium concentration was 0.2 ppm (μg/g) in thereaction raw material. At that time, quantitation limits of phosphorousand calcium in consideration of the result of a blank test were 0.4 ppmand 0.06 ppm, respectively.

Comparative Example 5

Production of fatty acid methyl ester and glycerin and measurement ofactivity of a solid catalyst were performed with use of the samematerials and through the same method as Example 5 except that theprocess for mixing palm oil and methanol and causing the mixture to passthe packed device was omitted in Comparative Example 5. In ComparativeExample 5, measurement of activity of MnTiO3 was performed when thereaction times were 216 hours, 408 hours, 599 hours, and 840 hours.

In Comparative Example 5, phosphorous concentration and calciumconcentration of the reaction raw material were 2.5 ppm (μg/g) and 1.0ppm (μg/g), respectively.

Further, the adsorber and the catalyst that have been subjected to thereaction for 1000 hours were analyzed through X-ray FluorescenceAnalysis (XRF). The result of the analysis showed that the catalystadsorbed 35 mg of phosphorous and phosphorous compounds and 7 mg ofcalcium and calcium compounds.

(Result of Measuring Activity of Solid Catalyst)

FIG. 3 illustrates the result of measuring activity of the solidcatalyst. FIG. 3 is a graph showing changes of conversion rates of palmoil and yields of fatty acid methyl ester at a time when reaction timeschange from 200 hours to 1000 hours. In FIG. 3, “black triangle”indicates the conversion rate of palm oil in Example 5, “white triangle”indicates the conversion rate of palm oil in Comparative Example 5,“black square” indicates the yield of fatty acid methyl ester in Example5, and “white square” indicates the yield of fatty acid methyl ester inComparative Example 5.

As illustrated in FIG. 3, in Example 5 where the reaction raw materialwas caused to pass the packed device in order to reduce phosphorousconcentration and calcium concentration of the reaction raw material,the conversion rate of palm oil and the yield of fatty acid methyl esterdropped only by approximately 3-5%, and did not change greatly.

In contrast thereto, in Comparative Example 5 where the reaction rawmaterial was not caused to pass the packed device and phosphorousconcentration and calcium concentration of the reaction raw materialwere not made lower than 2.5 ppm and 1 ppm, respectively, the conversionrate of palm oil and the yield of fatty acid methyl ester changedgreatly as the reaction time elapsed. The conversion rate of palm oildropped approximately two times larger than that in Example 5, and theyield of fatty acid methyl ester dropped approximately four times largerthan that in Example 5.

The results illustrated in FIG. 3 show that by reducing phosphorousconcentration and calcium concentration of the reaction raw material tobe less than 2.5 ppm and 1 ppm, respectively, it is possible to suppressthe drop of activity of MnTiO3.

Example 6

(Production of Fatty Acid Alkyl Ester and Glycerin)

In the present Example, palm oil and methanol were used as reaction rawmaterials. The palm oil was refined palm oil having been degummed. AnSUS 316 reactor (first reactor 10) of 10 mm in inner diameter and 210 mmin length was filled with a solid catalyst (15 mL).

Palm oil (6.3 g/hr) and methanol (6.3 g/hr) were continuously suppliedby a constant flow pump, heated at 200° C. and mixed by a line mixer,and then caused to flow downward from the upper part of the firstreactor 10. The inside of the first reactor 10 was set to have atemperature of 200° C. and a pressure of 5 MPa. In the present Example,a catalyst prepared in the same manner as Example 5 was used.

The reaction liquid obtained in the first reactor 10 was supplied to thefirst high pressure flash tower 11. The pressure of the first highpressure flash tower 11 was set to 0.35 MPa. Then, a heavy liquidcontinuously extracted from the bottom of the first high pressure flashtower 11 was supplied to the first low pressure flash tower 12. Theheavy liquid continuously extracted from the first high pressure flashtower 11 contained 17% of methanol.

The heavy liquid extracted from the bottom of the first low pressureflash tower 12 was separated into the upper phase and the lower phasewith use of a coalescer (oil-water separation film, first phaseseparator 14). Each phase was obtained as an even phase. The upper phasecontained 0.05% of glycerin.

Subsequently, the obtained upper phase (6.3 g/hr) was continuouslysupplied to the second reactor 20 and caused to react with methanol (6.3g/hr) under the same conditions (200° C., 5 MPa) as the first reactor10. The second reactor 20 was filled with 6 mL of the aforementionedsolid catalyst.

Then, the reaction liquid obtained in the second reactor 20 was suppliedto the second high pressure flash tower 21. The pressure of the secondhigh pressure flash tower 21 was set to 0.35 MPa. Then, the heavy liquidcontinuously extracted from the bottom of the second high pressure flashtower 21 was supplied to the second low pressure flash tower 22. Theheavy liquid continuously extracted from the second high pressure flashtower 21 contained 14% of methanol.

The heavy liquid extracted from the bottom of the second low pressureflash tower 22 and the lower phase (glycerin phase) in the first phaseseparator 14 were mixed with each other and supplied to a thin filmevaporator (alcohol evaporator 23) in order to diffuse unreactedmethanol contained in the mixture liquid. The inside of the thin filmevaporator was adjusted to have a pressure of 0.03 MPa and thetemperature of a heater was adjusted to be 175° C. The residence timewas set to 2 minutes. The heavy liquid continuously extracted from thebottom of the tower of the thin film evaporator contained 0.07% ofmethanol.

Then, the obtained heavy liquid was separated by a coalescer (oil-waterseparation film, second phase separator 24) into the upper phase and thelower phase. The obtained upper phase contained fatty acid methyl ester(whose purity was more than 99%) and the obtained lower phase containedglycerin (whose purity was more than 99%). Here, glycerin concentrationin the obtained upper phase was less than 0.05 wt % and monoglycerideconcentration in the obtained upper phase was 0.25 wt %. That is,concentration of fatty acid alkyl ester contained in the obtained upperphase was 99.7 wt %.

In the method of the present invention for producing fatty acid alkylester and/or glycerin, at least a part of heat of unreacted alcoholevaporated from a reaction liquid obtained by reacting fat and oil andalcohol over a solid catalyst is used in reproduction of alcohol.

Consequently, at least a part of energy required in the alcohol refiningstep is obtained inside the reaction system, and therefore it ispossible to reduce energy required to produce outside the reactionsystem. This yields an effect of reducing costs in producing fatty acidalkyl ester and glycerin over a solid catalyst.

The invention being thus described, it will be obvious that the same waymay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the invention, and all suchmodifications as would be obvious to one skilled in the art are intendedto be included within the scope of the following claims.

INDUSTRIAL APPLICABILITY

According to the method of the present invention for producing fattyacid alkyl ester and glycerin, it is possible to produce, cheaply,industrially, and environment-friendly, fatty acid alkyl esterapplicable to biodiesel fuel, foods, cosmetics, medicines, fuels etc.and glycerin applicable to nitroglycerin, raw materials for alkyd resin,medicines, foods, paints, cosmetics etc.

1. A method for producing fatty acid alkyl ester and/or glycerin,comprising: a first reaction step of reacting fat and oil with alcoholover a solid catalyst; a first alcohol stripping step of evaporating,from a first reaction liquid obtained in the first reaction step,unreacted alcohol that remains without reacting in the first reactionstep; and an alcohol refining step of refining the alcohol from theunreacted alcohol with use of at least a part of heat of the unreactedalcohol.
 2. The method as set forth in claim 1, wherein at least twostages of pressures that are different from each other are applied inthe first alcohol stripping step.
 3. The method as set forth in claim 2,wherein a first stage of the pressures in the first alcohol strippingstep ranges from 0.15 to 1.5 MPa.
 4. The method as set forth in claim 1,further comprising: a second reaction step of reacting fat and oil withalcohol over a solid catalyst, the fat and oil being contained in anupper phase obtained by phase-separating refined products obtained inthe first alcohol stripping step; and a second alcohol stripping step ofevaporating, from a second reaction liquid obtained in the secondreaction step, unreacted alcohol that remains without reacting in thesecond reaction step, in the alcohol refining step, the alcohol beingrefined from the unreacted alcohol evaporated in the first and secondalcohol stripping steps, with use of at least a part of heat of theunreacted alcohol.
 5. The method as set forth in claim 4, wherein atleast two stages of pressures that are different from each other areapplied in the second alcohol stripping step.
 6. The method as set forthin claim 5, wherein a first stage of the pressures in the second alcoholstripping step ranges from 0.15 to 1.5 MPa.
 7. The method as set forthin claim 1, wherein a substance that is contained in the alcoholobtained in the alcohol refining step and that is other than the alcoholaccounts for not more than 1000 ppm of all components contained in thealcohol obtained in the alcohol refining step.
 8. The method as setforth in claim 1, further comprising: a first phase-separation step ofphase-separating the first reaction liquid obtained in the firstreaction step into a first fatty acid alkyl ester phase and a firstglycerin phase; a second reaction step of reacting fat and oil containedin the first fatty acid alkyl ester phase with alcohol over a solidcatalyst; a third alcohol stripping step of evaporating, from a secondreaction liquid obtained in the second reaction step, unreacted alcoholthat remains without reacting in the second reaction step, with use ofan evaporator including a heat exchanger selected from a thin filmevaporator with an agitating rotor, a thin film evaporator with tubesarranged as a bundle, and a thin film evaporator with a centrifugalrotor; and a second phase-separation step of phase-separating refinedproducts obtained in the third alcohol stripping step into a secondfatty acid alkyl ester phase and a second glycerin phase.
 9. The methodas set forth in claim 1, further comprising: a first phase-separationstep of phase-separating the first reaction liquid obtained in the firstreaction step into a first fatty acid alkyl ester phase and a firstglycerin phase; a second reaction step of reacting fat and oil containedin the first fatty acid alkyl ester phase with alcohol over a solidcatalyst; a third alcohol stripping step of evaporating, from a secondreaction liquid obtained in the second reaction step, unreacted alcoholthat remains without reacting in the second reaction step, with use ofan evaporator including a heat exchanger whose residence time is 20minutes or less; and a second phase-separation step of phase-separatingrefined products obtained in the third alcohol stripping step into asecond fatty acid alkyl ester phase and a second glycerin phase.
 10. Themethod as set forth in claim 8, wherein in the third alcohol strippingstep, the unreacted alcohol that remains without reacting in the firstreaction step is further evaporated from the first glycerin phase withuse of the evaporator.
 11. The method as set forth in claim 8, whereinin the third alcohol stripping step, the unreacted alcohol that remainswithout reacting in the second reaction step is evaporated from thesecond reacting liquid obtained in the second reaction step, and theunreacted alcohol that remains without reacting in the first reactionstep is evaporated from the first glycerin phase.
 12. The method as setforth in claim 8, wherein a second alcohol stripping step of evaporatingunreacted alcohol from the second reaction liquid is performed beforethe third alcohol stripping step.
 13. The method as set forth in claim8, wherein the first alcohol stripping step is performed before thefirst phase-separation step.
 14. The method as set forth in claim 8,wherein in the third alcohol stripping step, the unreacted alcohol isevaporated in such a manner that the unreacted alcohol accounts for notmore than 0.5 wt % of the refined products obtained in the third alcoholstripping step.
 15. The method as set forth in claim 1, furthercomprising a removal step of removing at least one selected fromphosphorous, phosphorous compounds, calcium, and calcium compounds thatare contained in a reaction raw material including the fat and oil andthe alcohol.
 16. The method as set forth in claim 15, wherein in theremoval step, at least one selected from phosphorous, phosphorouscompounds, calcium, and calcium compounds is adsorbed and removed by anadsorber.
 17. The method as set forth in claim 15, wherein in theremoval step, concentration of phosphorous atoms in phosphorous andphosphorous compounds contained in the reaction raw material is lessthan 2.5 ppm.
 18. The method as set forth in claim 15, wherein in theremoval step, concentration of calcium atoms in calcium and calciumcompounds contained in the reaction raw material is less than 1 ppm. 19.The method as set forth in claim 1, further comprising: a firstphase-separation step of phase-separating a refined product into a firstfatty acid alkyl ester phase and a first glycerin phase with use of aseparation filter, the refined product being obtained by evaporating theunreacted alcohol from the first reaction liquid in the first alcoholstripping step; a second reaction step of reacting fat and oil containedin the first fatty acid alkyl ester phase with alcohol over a solidcatalyst; and a second phase-separation step of phase-separating asecond reaction liquid obtained in the second reaction step into asecond fatty acid alkyl ester phase and a second glycerin phase with useof a separation filter.
 20. A device for producing fatty acid alkylester and/or glycerin, comprising: a reactor for reacting fat and oilwith alcohol over a solid catalyst; a stripper for stripping, from areaction liquid obtained in the reactor, unreacted alcohol that remainswithout reacting in the reactor; and a refiner for refining the alcoholfrom the unreacted alcohol stripped in the stripper, with use of atleast a part of heat of the unreacted alcohol.
 21. The device as setforth in claim 20, further comprising a packed device filled with anadsorber for adsorbing at least one selected from phosphorous,phosphorous compounds, calcium, and calcium compounds that are containedin a reaction raw material including the fat and oil and the alcohol,the reactor causing the reaction raw material having passed the packeddevice to react over a solid catalyst.